EP0217212A2 - Semipermeable composite membrane and process for preparation thereof - Google Patents
Semipermeable composite membrane and process for preparation thereof Download PDFInfo
- Publication number
- EP0217212A2 EP0217212A2 EP19860112706 EP86112706A EP0217212A2 EP 0217212 A2 EP0217212 A2 EP 0217212A2 EP 19860112706 EP19860112706 EP 19860112706 EP 86112706 A EP86112706 A EP 86112706A EP 0217212 A2 EP0217212 A2 EP 0217212A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- preparation
- semipermeable composite
- semipermeable
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 151
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 24
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 239000000470 constituent Substances 0.000 claims abstract description 24
- 239000004952 Polyamide Substances 0.000 claims abstract description 14
- 229920002647 polyamide Polymers 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 239000002253 acid Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 150000004820 halides Chemical class 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000001294 propane Substances 0.000 claims description 12
- 239000001488 sodium phosphate Substances 0.000 claims description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 150000003335 secondary amines Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- -1 isophthaloyl halides Chemical class 0.000 claims description 10
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000012696 Interfacial polycondensation Methods 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229920006037 cross link polymer Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims 2
- 229920003235 aromatic polyamide Polymers 0.000 claims 2
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 35
- 230000004907 flux Effects 0.000 description 32
- 150000003839 salts Chemical class 0.000 description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 28
- 239000000460 chlorine Substances 0.000 description 28
- 229910052801 chlorine Inorganic materials 0.000 description 28
- 238000012360 testing method Methods 0.000 description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 238000001223 reverse osmosis Methods 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 11
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 11
- 235000019801 trisodium phosphate Nutrition 0.000 description 11
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 4
- 229940081735 acetylcellulose Drugs 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000004193 piperazinyl group Chemical group 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/24998—Composite has more than two layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31536—Including interfacial reaction product of adjacent layers
Definitions
- the present invention relates to a semipermeable membrane for selective permeation and separation of a specific component in a liquid mixture. More particularly, the present invention relates to a high-performance semipermeable composite membrane which can be used for desalting brakish water to obtain portable water, for removing or recovering a contaminant or useful substance from waste water causing environmental pollution, such as dyeing waste water or electro-deposition paint waste water, to enable a closed system for the treatment of waste water and for producing ultra pure water to be used for the production of semiconductors.
- an asymmetric membrane formed of acetyl cellulose for example, a Loeb type membrane disclosed in the specification of U.S. Patent No. 3,l33,l32 or U.S. Patent No. 3,l33,l37.
- This membrane has problems in connection with the hydrolysis resistance, the microbiological resistance and the chemical resistance, and if it is intended to improve the permeability, a membrane having a good pressure resistance and durability cannot be obtained. Accordingly, membranes of this type are not practically broadly used though they are used in much limited regions. Research works have been made with a view to developing new materials free from these defects of the asymmetric membrane of acetyl cellulose, mainly in the U.S.A.
- a composite membrane As a semipermeable membrane of a type different from the Loeb type membrane, a composite membrane has been developed comprising a microporous substrate and an active layer substantially deciding a membrane performance, which covers the microporous substrate.
- materials suitable for the intended use can be selected for the active layer and microporous substrate, and the freedom of the membranepreparation technique is increased.
- the composite membrane can said to be stored in the dry state.
- This composite membrane is divided into two types, that is, a type comprising an active layer coated on a microporous substrate through a gelled layer, and a type comprising an active layer coated directly on a microporous substrate.
- Specific examples of the former type are disclosed in Japanese Unexamined Patent Publication No. 49-l33282, Japanese Examined Patent Publication No. 55-38l64, PB Report 80-l82090, Japanese Examined Patent Publication No. 59-27202, and Japanese Unexamined Patent Publication No. 56-40403. It is thought that the preparation of the membrane of the former type is easier than the preparation of the membrane of the latter type and much research has been made into the membrane of the former type.
- membranes of the latter type there can be mentioned membranes disclosed in the specification of U.S. Patent No. 3,744,642, the specification of U.S. Patent No. 3,926,798, Japanese Unexamined Patent Publication No. 55-l47l06, the specification of U.S. Patent No. 4,277,344, and Japanese Unexamined Patent Publication No. 58-24303.
- the composite membrane of this type if a high permeability is desired, since the active layer is coated very thinly, defects are readily formed by flaws or foreign substances on the microporous supporting membrane, and it is considered generally difficult to manufacture a high-performance membrane stably with good reproducibility on an industrial scale.
- a semipermeable composite membrane comprising a microporous substrate and an ultra-thin membrane covering the substrate wherein the ultra-thin membrane comprises a crosslinked piperazine polyamide as a main component and contains a constituent component represented by the following formula [I] wherein R stands for -H or -CH3 and n is an integer of from 0 to 3.
- a process for the preparation of semipermeable composite membranes which comprises forming an ultra-thin membrane on a microporous substrate by interfacial polycondensation using an aqueous solution containing piperazine and a secondary amine represented by the following formula [III]: wherein R stands for -H or -CH3 and n is an integer of from 0 to 3, and a solution of a polyfunctional acid halide in a water-immiscible organic solvent, wherein at least one member selected from the group consisting of compounds represented by the following formulae [IV], [V] and [VI]: wherein n is l or 2, A and A,, which may be the same or different, stand for an aliphatic, or aromatic hydrocarbon group, and X stands for -CH2-, -O- or -S-, and wherein B stands for an aliphatic hydrocarbon group and n is an integer of from l to 6, is incorporated in said
- the ultra-thin membrane is composed of a crosslinked polyamide formed by interfacial polycondensation, which comprises a cross-linked piperazine polyamide having a constituent component of the formula as a main component and contains a constituent component represented by the formula [I], and which shows a substantial separating capacity.
- the thickness of the ultra-thin membrane may be optionally chosen in the range of from l0 nm to l,000 nm according to the intended object. However, if the thickness is small, flaws are readily formed, and if the thickness is large, the water permeation rate is reduced. Accordingly, preferably the thickness of the ultra-thin layer is 20 nm to 300 nm.
- the crosslinked piperazine polyamide used in the present invention is a crosslinked polymer comprising as main components a constituent component of the formula a substituted and/or unsubstituted aromatic ring, and an amide linkage connecting therebetween them, and this crosslinked polymer is disclosed in the specification of U.S. Patent No. 4,259,l83, PB Report 288387, and PB Report 80-l2757.
- a constituent component represented by the formula [I] in addition to the above-mentioned constituent components, a high salt rejection can be attained.
- constituent component represented by the formula I for example, there can be mentioned but in view of the performance of the composite semipermeable membrane, most preferable.
- the ratio between and the constituent component represented by the formula [I] is not particularly critical, but in view of the performance of the semipermeable composite membrane, preferably the amount of the constituent component of the formula [I] is 0.05 to 0.5 part by weight per part by weight of the piperazine ring
- a constituent component having as main recurring units those represented by the following formula [II] is preferred:
- the content of the constituent component represented by the formula II is not particularly critical, but in view of the performance of the semipermeable composite membrane, preferably the amount of the constituent component of the formula [II] is 0.l to l.0 part by weight per part by weight of the piperazine ring
- the kind and position of the substituent on the aromatic ring is not particularly critical.
- the substituent there may be optionally used lower alkyl groups such as methyl and ethyl groups, a methoxy group, an ethoxy group, a sulfonic acid group, sulfonic acid ester groups, a carboxylic acid group, carboxylic acid ester groups, an acyl group, halogens such as fluorine, chlorine, bromine and iodine, and a nitro group.
- a methoxy group, a sulfonic acid group, and a carboxylic acid group are preferred.
- the position of the substituent is not particularly critical, but steric intricacy is not preferred.
- R stands for a substituent such as a methoxy, sulfonic acid or carboxylic acid group.
- the aromatic ring constituent component comprises at least one member selected from the group consisting of components represented by the following formulae:
- the group forming a covalent bond with the nitrogen atom there can be mentioned a hydrogen atom forming a secondary amino group or carbonyl group forming an amide linkage.
- the group forming a covalent bond with the sulfur atom (-SO2-), there can be mentioned a hydroxyl group forming a sulfonic acid group or an amino group forming a sulfonamide linkage.
- an ultra-thin film be formed by interfacial polycondensation using piperazine, a secondary amine represented by the following formula [III]: wherein R stands for -H or -CH3 and n is an integer of from 0 to 3, if desired, a polyaminoether having recurring units represented by the following formula [VII]: and an aromatic ring-containing polyfunctional acid halide represented by the following formula: wherein X stands for -Cl, -Br, -I or -F.
- the microporous substrate has no substantial separation capacity and exerts a function to support the above-mentioned ultra-thin membrane.
- the substrate has to have uniform fine pores or has fine pores of a size which is gradually increased from one surface toward the other surface.
- the pore size is preferably about l0 to about l00 nm.
- the microporous substrate may be selected from commercially available materials such as Milipore Filter VSWP and Toyo Filter Paper UKl0, but ordinarily, the microporous substrate can be prepared according to the process disclosed in Office of Saline Water/Research and Development Progress Report, No. 359 (l968).
- a microporous substrate the majority of the surface of which has fine pores having a diameter smaller than several ten nm, can be obtained by casting a solution of polysulfone in dimethylformamide (DMF) in a certain thickness on a densely woven polyester fabric or a nonwoven fabric and coagulating the polymer in an aqueous solution containing 0.5% by weight of sodium dodecyl sulfate and 2% by weight of DMF.
- DMF dimethylformamide
- the ultra-tine membrane having a substantial separation capacity in the semipermeable composite membrane of the present invention is formed by interfacial polycondensation using an aqueous solution of piperazine and the above-mentioned secondary amine represented by the formula [III] (hereinafter referred to as "composition") and a solution of the polyfunctional acid halide in a water-immiscible organic solvent.
- composition aqueous solution of piperazine and the above-mentioned secondary amine represented by the formula [III] (hereinafter referred to as "composition") and a solution of the polyfunctional acid halide in a water-immiscible organic solvent.
- composition aqueous solution of piperazine and the above-mentioned secondary amine represented by the formula [III]
- the present invention is characterized in that an additive is incorporated into the above-mentioned composition so as to greatly improve the water flux of the semipermeable composite membrane.
- alkyldiphenylether disulfonate sodium alkyldiphenylether disulfonate, methylene-bis(sodium naphthalene-sulfonate) and sorbitol are preferred, and alkyldiphenyletherdisulfonic acid disodium salt is especially preferred because the performance of the composite semipermeable membrane is improved and it also acts as a surface active agent described below in the composition.
- a dodecyl group is preferred as the alkyl group, but practically, another alkyl group may be mixed with the dodecyl group, and two or more alkyl groups may be present.
- an alkaline metal compound such as trisodium phosphate.
- the semipermeable composite membrane is prepared by coating the above-mentioned composition on at least one surface of a microporous substrate, air-drying and/or heating the coated membrane to evaporate a part or all of water, and coating a solution of a polyfunctional acid halide as the main component in a water immiscible organic solvent incapable of dissolving the porous substrate on the coated surface of membrane to undergo crosslinking reaction, followed by drying.
- composition for forming the semipermeable composite membrane of the present invention comprises preferably piperazine and l,3-di-(4-piperidyl)-propane of the following formula:
- the concentration of these components is 0.l to l0% by weight, preferable l to 4% by weight, and the mixing ratio between piperazine and l,3-di-(4-piperidyl)-propane is preferably such that the amount of l,3-di-(4-piperidyl)-propane is 0.05 to 0.5 part by weight per part by weight of piperazine.
- the mixing ratio between piperazine and the polyaminoether having recurring units of the formula [VII] is preferably such that the amount of the polyaminoether is 0.l to l.0 part by weight per part by weight of piperazine.
- a surface active agent especially an anionic surface active agent
- sodium dodecyl sulfate and sodium alkylbenzenesulfonate may be used, and alkyldiphenyletherdisulfonic acid disodium salt is especially effective for obtaining a membrane with good performance.
- the surface active agent is used in an amount of 0.0l to 4% by weight.
- a water-soluble organic solvent not degrading the microporous organic solvent may be added to the composition.
- an alkaline metal salt for example, a hydrochloric acid scavenger such as trisodium phosphate or sodium hydroxide
- a hydrochloric acid scavenger such as trisodium phosphate or sodium hydroxide
- Trisodium phosphate is especially preferred in view of the improvement of the water flux of the semipermeable composite membrane.
- any of polyfunctional acid halides capable of reacting with the secondary amine to form a crosslinked polyamide as the ultra-thin membrane can be used.
- aromatic polyfunctional acid halides such as trimesoyl halide, benzophenonetetracarboxylic acid halide, trimellitic acid halide, pyromellitic acid halide, isophthaloyl halide, terephthaloyl halide, naphthalenedicarboxylic acid halide, diphenyldicarboxylic acid halide, pyridinedicarboxylic acid halide, benzenedisulfonyl halide, and chlorosulfonylisophthaloyl halides can be used.
- the mixing ratio of the acid chlorides is not particularly critical.
- the trimesoyl chloride/isophthaloyl chloride or trimesoyl chloride/terephthaloyl chloride weight ratio is preferably from l/0 to 3/7, and single use of isophthaloyl chloride or terephthaloyl chloride is not preferred in view of the water flux.
- the polyfunctional acid halide is generally used in the state dissolved in an organic solvent at a concentration of 0.0l to 2.0% by weight, preferably 0.l to 0.5% by weight.
- the organic solvent used in the present invention should be immiscible with water, be capable of dissolving the acid chloride therein, and not damage or destroy the microporous substrate and any organic solvent capable of providing a crosslinked polyamide by interfacial polymerization can be used.
- hydrocarbon compounds cyclohexane, and trichlorotrifluoroethane may be preferably used.
- at least one member selected from n-hexane and trifluorotrichloroethane is preferably used, and when the safety problem, that is, ignitability, is further taken into consideration, trichlorotrifluoroethane is especially preferred.
- any known coating means can be adopted for coating the composition on the microporous supporting membrane.
- a method in which the composition is coated on the substrate and a method in which the substrate is dipped in the composition.
- the method in which the composition is coated on the substrate is preferred because one surface of the microporous substrate can be uniformly coated with the composition and the operation can be easily accomplished.
- a means such that the composition does not adhere to the other surface of the microporous supporting membrane at the coating step.
- a liquid-removing step is arranged to remove the excessive composition applied at the coating step.
- the liquid-removing means there may be adoped, for example, a method in which the membrane surface is held vertically to allow the composition to naturally flow down.
- the coated porous substrate is air-dried or heated in an oven at room temperature to l50°C.
- the drying period is changed according to the drying method, that is, the manner of introduction of heat or the kind of oven drier, but the drying period is generally within the range of from 0.5 minute to 60 minutes.
- the solution of the polyfunctional acid halide in the water-immiscible organic solvent is coated on the substrate and after the liquid-removing operation, the coated membrane is air-dried or heated to obtain a semipermeable composite membrane.
- the drying operation is ordinarily carried out at room temperature to l50°C, and the drying time is determined according to the drying temperature. This drying or heating treatment is effective for preventing peeling of the ultra-thin membrane from the microporous substrate.
- the so-obtained semipermeable composite membrane can be used as it is.
- the surface of the ultra-thin membrane of the semipermeable composite membrane can be covered with a protecting polymer membrane, and this protection is practically preferred.
- Application of the protective membrane on the surface of the ultra-thin membrane is accomplished by coating an appropriate polymer solution, followed by drying.
- the protecting polymer there can be mentioned, for example, water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, and polyvinyl pyrrolidone. In view of the strength of the protecting membrane, polyvinyl alcohol is especially preferred.
- the polymer is generally used in the form of an aqueous solution having a concentration of 0.5 to l0% by weight. Not only a dip-coating method but also a spray-coating method or a brush-coating method can be adopted for coating the polymer solution.
- the coated semipermeable composite membrane is dried in an oven to obtain a final product. It is generally preferred that the drying operation be carried out at 60 to l20°C for 2 to l0 minutes.
- the sodium chloride rejection as the selective separation capacity was determined according to the customary method of measuring the electroconductivity. Furthermore, the water flux as the permeation capacity was determined by measuring the amount of water permeation per unit area per unit hour.
- DMF dimethylformamide
- FR-PS fiber-reinforced polysulfone substrate
- the FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 0.5% by weight of sodium dodecyl sulfate, and l.0% by weight of trisodium phosphate, and was air-dried at room temperature for 2 minutes.
- composition containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 0.5% by weight of sodium dodecyl sulfate, and l.0% by weight of trisodium phosphate
- the FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 0.5% by weight of sodium dodecyl sulfate, and l.0% by weight of trisodium phosphate, and was dried for l minute at 70°C.
- the FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 0.5% by weight of dodecyldiphenyletherdisulfonic acid disodium salt, and l.0% by weight of trisodium phosphate, and was dried for l minute with hot air at 70°C. Then, the substrate was coated with a solution obtained by dissolving 0.5%by weight of trimesoyl chloride in trichlorotrifluoroethane and heat-treated for 5 minutes at l00°C.
- the salt rejection was 83% and the water salt rejection was 2.2m3/m2 ⁇ day, and after the heat resistance test, the salt rejection was 82% and the water flux was 2.2m3/m2 ⁇ day. It was found that the membrane performance was not substantially changed. Thus, it was confirmed that the membrane had good hydrogen peroxide resistance and good heat resistance.
- the reverse osmosis test was carried out under a pressure of l5 kg/cm2 at 25°C by using an aqueous solution containing 0.l% of isopropyl alcohol as the feed water, and when the test was conducted for l2 hours, the isopropyl alcohol rejection was measured by gas chromatography. It was found that the rejection was 59%.
- an aqueous solution containing 0.2% of MgS04, 0.l5% of MgCl2 or 0.2% of Na2SO4 was used as the feed water and the salt rejection was measured in the same manner as described above with respect to the removal of NaCl.
- the MgSO4 rejection was 99.5%
- the MgCl2 rejection was 95%
- the Na2SO4 rejection was 99.9%.
- the FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidinyl)-propane, 0.3% by weight of water-soluble polyaminoether, 0.5% by weight of dodecyldiphenyletherdisulfonic acid disodium salt, and l.0% by weight of trisodium phosphate, and was dried for l minute with hot air at 70°C.
- composition containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidinyl)-propane, 0.3% by weight of water-soluble polyaminoether, 0.5% by weight of dodecyldiphenyletherdisulfonic acid disodium salt, and l.0% by weight of trisodium phosphate, and was dried for l minute with hot air at 70°C
- the membrane was coated with a solution of 5% by weight of trimesoyl chloride in trichlorotrifluoroethane and was heat-treated for 5 minutes with hot air at l00°C.
- the salt rejection was 84% and the water flux was 2.7 m3/m2 ⁇ day.
- Chlorine was added to the feed water so that the residual chlorine concentration was l ppm and the pH value was 6.5, and the test was conducted for 5 hours. It was found that the salt rejection was 94% and the water flux was 2.4 m3m2 ⁇ day.
- the FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 2.0% by weight of dodecyldiphenyletherdisulfonic acid disodium salt, and l.0% by weight of trisodium phosphate, and was dried for 30 seconds with hot air at 80°C. Then, the membrane was coated with a solution of 0.5% by weight of trimesoyl chloride in trichlorotrifluoroethane and was heat-treated for 5 minutes at l00°C.
- the obtained composite membrane was subjected to the reverse osmosis test under a pressure of 7.5 kg/cm2 at a temperature of 25°C and a pH value 30of 6.5 by using an aqueous solution containing 0.05% of NaCl as the feed water.
- the salt rejection was 82% and the water was 2.l m3/m2 ⁇ day
- Example l9 The procedures of Example l9 were repeated in the same manner except that 2% of hydrogen peroxide was added to the feed water instead of chlorine. The operation was conducted under a pressure of 2 kg/cm2 for l2 hours and the hydrogen peroxide was removed. Then, the reverse osmosis test was carried out under a pressure of 7.5 kg/cm2 at 25°C by using an aqueous solution containing 0.05% of NaCl as the feed water. The obtained results are shown in Table 4.
- the membrane prepared in the same manner as described in Example l4 was subjected to the chlorine resistance test. Namely, chlorine was added to a 0.05% NaCl aqueous solution as the feed water so that the residual chlorine content was l0 ppm and the pH value was 6.5, and the operation was conducted for l00 hours under a pressure of 7.5 kg/cm2. Then, the residual chlorine content was changed to 50 ppm and the operation was conducted for ll5 hours. Then, the residual chlorine content was changed to l00 ppm and the operation was conducted for l20 hours.
- the salt rejection was 82% and the water flux was 2.0 m3/m2 ⁇ day, and after the addition of chlorine, the salt rejection was 80% and the water flux was l.8 m3/m2 ⁇ day. No substantial deterioration of the membrane was observed.
- the membrane prepared in the same manner as described in Example l9 was subjected to the reverse osmosis test using isopropyl alcohol or an inorganic salt other than NaCl. The obtained results are shown in Table 5.
- Example l4 The composite membrane obtained in Example l4 was cut to an appropriate size and immersed in methylene chloride to separate the ultra-thin membrane layer from the supporting membrane.
- the ultra-thin membrane was recovered by suction filtration using a glass filter. Then, 30 mg of the recovered sample was hydrolyzed with l2 ml of 6N hydrochloric acid at l80°C.
- the liquid left after the removal of insoluble solids was dried to a solid state and the weight was measured. It was found that the weight was 25 mg.
- the solid was dissolved in a mixed solvent comprising 2 ml of methyl alcohol and l0 ml of ethyl ether and diazomethane was bubbled to the solution to esterify by methylation.
- the solvent was removed by distillation under reduced pressure, and 2 ml of methyl acetate and 0.5 ml of trifluoroacetic acid anhydride were added and left for 5 minutes.
- the solvent was removed by distillation under reduced pressure, the residue was dissolved in l ml of methyl alcohol, and the composition was analyzed by the GC-MS method.
- the preparation of the membrane and the reverse osmosis test were carried out in the same manner as in Comparative Example 3 except that after coating of the trichlorofluoroethane solution of the acid halide, the coated membrane was heat-treated for 5 minutes at l00°C. It was found that the salt rejection was 55% and the water flux was 2.0 m3/m2 ⁇ day.
- the composite membrane of the present invention is for selective permeation and separation of a specific component in a liquid mixture and is used for desalting brakish water or producing ultra pure water for the production of semiconductors.
- the composite membrane has a high desalting and high water flux such that can rarely be attained by the conventional techniques. Furthermore, a membrane having good chlorine resistance and good hydrogen peroxide resistance can be provided.
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Abstract
Description
- The present invention relates to a semipermeable membrane for selective permeation and separation of a specific component in a liquid mixture. More particularly, the present invention relates to a high-performance semipermeable composite membrane which can be used for desalting brakish water to obtain portable water, for removing or recovering a contaminant or useful substance from waste water causing environmental pollution, such as dyeing waste water or electro-deposition paint waste water, to enable a closed system for the treatment of waste water and for producing ultra pure water to be used for the production of semiconductors.
- As the semipermeable membrane heretofore industrially used, there can be mentioned an asymmetric membrane formed of acetyl cellulose, for example, a Loeb type membrane disclosed in the specification of U.S. Patent No. 3,l33,l32 or U.S. Patent No. 3,l33,l37. This membrane has problems in connection with the hydrolysis resistance, the microbiological resistance and the chemical resistance, and if it is intended to improve the permeability, a membrane having a good pressure resistance and durability cannot be obtained. Accordingly, membranes of this type are not practically broadly used though they are used in much limited regions. Research works have been made with a view to developing new materials free from these defects of the asymmetric membrane of acetyl cellulose, mainly in the U.S.A. and Japan. Materials in which some defects are eliminated, such as polyamides, polyamide-hydrazides (see the specification of U.S. Patent No. 3,567,632), polyamide acids (see Japanese Examined Patent Publication No. 55-37282), closslinked polyamide acids (see Japanese Examined Patent Publication No. 56-3769), polyimidazopyrrolones, polysulfonamides, polybenzimidazoles, polybenzimidazolones, and polyarylene oxides, have been developed, but their selective separating property or permeability are inferior to those of the acetyl cellulose membrane.
- As a semipermeable membrane of a type different from the Loeb type membrane, a composite membrane has been developed comprising a microporous substrate and an active layer substantially deciding a membrane performance, which covers the microporous substrate. In this composite membrane, materials suitable for the intended use can be selected for the active layer and microporous substrate, and the freedom of the membranepreparation technique is increased. Furthermore, although the Loeb type membrane must be stored in the wet state, the composite membrane can said to be stored in the dry state.
- This composite membrane is divided into two types, that is, a type comprising an active layer coated on a microporous substrate through a gelled layer, and a type comprising an active layer coated directly on a microporous substrate. Specific examples of the former type are disclosed in Japanese Unexamined Patent Publication No. 49-l33282, Japanese Examined Patent Publication No. 55-38l64, PB Report 80-l82090, Japanese Examined Patent Publication No. 59-27202, and Japanese Unexamined Patent Publication No. 56-40403. It is thought that the preparation of the membrane of the former type is easier than the preparation of the membrane of the latter type and much research has been made into the membrane of the former type. However, when the membrane is used for the reverse osmosis under a low pressure, the water permeability is reduced and a satisfactory performance cannot be obtained. Moreover, it is difficult to obtain a membrane having enough chlorine resistance, which is an important factor for practical application to the reverse osmosis.
- As specific examples of the membrane of the latter type, there can be mentioned membranes disclosed in the specification of U.S. Patent No. 3,744,642, the specification of U.S. Patent No. 3,926,798, Japanese Unexamined Patent Publication No. 55-l47l06, the specification of U.S. Patent No. 4,277,344, and Japanese Unexamined Patent Publication No. 58-24303. In the composite membrane of this type, if a high permeability is desired, since the active layer is coated very thinly, defects are readily formed by flaws or foreign substances on the microporous supporting membrane, and it is considered generally difficult to manufacture a high-performance membrane stably with good reproducibility on an industrial scale. However, most membranes having chlorine resistance, heat resistance, and chemical resistance are those of the latter type. As the chlorine-resistant membrane, a piperazine type membrane (see the specification of U.S. Patent No. 4,l29,559) has attracted attention, and especially, a high water flux composite membrane composed of piperazine crosslinked with an aromatic polyfunctional acid halide has been proposed and has also attracted attention (see, for example, National Publication No. 56-50006, the specification of U.S. Patent No. 4,259,l83, and PB Report 288387). This membrane is excellent in that the water permeability is high even under a low pressure. However, the membrane is defective in that the sodium chloride rejection is relatively low, e.g., about 50%. In the desalination process and the production of ultra pure water for the production of semiconductors, a membrane having a high sodium chloride rejection is now desired, and improvements of the piperazine type composite membrane are proposed (see, for example, Japanese Unexamined Patent Publication No. 59-l79l03 and Japanese Examined Patent Publication No. 6l-27083). These improvements, however, are not satisfactory because the water permeability is reduced, and a membrane exceeding the above-mentioned piperazine type composite membrane has not been developed.
- We carried out research with a view to developing a semipermeable composite membrane showing a high salt rejection and a high water flux even under a low pressure and having an oxidation resistance, by improving the above-mentioned piperazine type membrane (disclosed in the specification of U.S. Patent No. 4,259,l83). As a result, it was found that a high salt rejection can be obtained by combining piperazine with a polyfunctional secondary amine having a specific ring structure, and if a specific additive is used for the production of this semipermeable composite membrane, a high water flux can be obtained. We have now completed the present invention based on this finding.
- More specifically, in accordance with one fundamental aspect of the present invention, there is provided a semipermeable composite membrane comprising a microporous substrate and an ultra-thin membrane covering the substrate wherein the ultra-thin membrane comprises a crosslinked piperazine polyamide as a main component and contains a constituent component represented by the following formula [I]
- In accordance with another fundamental aspect of the present invention, there is provided a process for the preparation of semipermeable composite membranes, which comprises forming an ultra-thin membrane on a microporous substrate by interfacial polycondensation using an aqueous solution containing piperazine and a secondary amine represented by the following formula [III]:
and a solution of a polyfunctional acid halide in a water-immiscible organic solvent, wherein at least one member selected from the group consisting of compounds represented by the following formulae [IV], [V] and [VI]:
is incorporated in said aqueous solution. - In the present invention, the ultra-thin membrane is composed of a crosslinked polyamide formed by interfacial polycondensation, which comprises a cross-linked piperazine polyamide having a constituent component of the formula
- The crosslinked piperazine polyamide used in the present invention is a crosslinked polymer comprising as main components a constituent component of the formula
-
- The ratio between
- Furthermore, a polymer may be added as another constituent component, and this polymer is effective for solving the problem of formation of defects by flaws or foreign substances on the microporous substrate. However, a polymer causing drastical degradation of the performance of the semipermeable composite membrane should be avoided. A constituent component having as main recurring units those represented by the following formula [II] is preferred:
- The content of the constituent component represented by the formula II is not particularly critical, but in view of the performance of the semipermeable composite membrane, preferably the amount of the constituent component of the formula [II] is 0.l to l.0 part by weight per part by weight of the piperazine ring
- In the foregoing description, the kind and position of the substituent on the aromatic ring is not particularly critical. As the substituent, there may be optionally used lower alkyl groups such as methyl and ethyl groups, a methoxy group, an ethoxy group, a sulfonic acid group, sulfonic acid ester groups, a carboxylic acid group, carboxylic acid ester groups, an acyl group, halogens such as fluorine, chlorine, bromine and iodine, and a nitro group. In view of the separating performance of the membrane and the membrane-forming property, a methoxy group, a sulfonic acid group, and a carboxylic acid group are preferred. The position of the substituent is not particularly critical, but steric intricacy is not preferred. For example, the following structures can be mentioned:
-
- In the foregoing constituent components, as the group forming a covalent bond with the nitrogen atom (>N-), there can be mentioned a hydrogen atom forming a secondary amino group or carbonyl group forming an amide linkage. As the group forming a covalent bond with the carbon atom (>C=O), there can be mentioned a hydroxyl group forming a carboxylic acid group or an amino group forming an amide linkage. As the group forming a covalent bond with the sulfur atom (-SO₂-), there can be mentioned a hydroxyl group forming a sulfonic acid group or an amino group forming a sulfonamide linkage.
- The method for incorporating these constituent components into the ultra-thin membrane having a substantial separating capacity is not.particularly critical. However, in view of the handling property of the starting material and the ease of the membrane-forming operation, it is preferred that an ultra-thin film be formed by interfacial polycondensation using piperazine, a secondary amine represented by the following formula [III]:
if desired, a polyaminoether having recurring units represented by the following formula [VII]: - In the present invention, the microporous substrate has no substantial separation capacity and exerts a function to support the above-mentioned ultra-thin membrane. The substrate has to have uniform fine pores or has fine pores of a size which is gradually increased from one surface toward the other surface. On one surface of the substrate, the pore size is preferably about l0 to about l00 nm. The microporous substrate may be selected from commercially available materials such as Milipore Filter VSWP and Toyo Filter Paper UKl0, but ordinarily, the microporous substrate can be prepared according to the process disclosed in Office of Saline Water/Research and Development Progress Report, No. 359 (l968). As the material, there may be used homopolymers such as polysulfone, acetyl cellulose, nitrocellulose, polyvinyl chloride, and blends thereof. For example, a microporous substrate, the majority of the surface of which has fine pores having a diameter smaller than several ten nm, can be obtained by casting a solution of polysulfone in dimethylformamide (DMF) in a certain thickness on a densely woven polyester fabric or a nonwoven fabric and coagulating the polymer in an aqueous solution containing 0.5% by weight of sodium dodecyl sulfate and 2% by weight of DMF.
- The preparation process according to the second aspect of the present invention will now be described.
- The ultra-tine membrane having a substantial separation capacity in the semipermeable composite membrane of the present invention is formed by interfacial polycondensation using an aqueous solution of piperazine and the above-mentioned secondary amine represented by the formula [III] (hereinafter referred to as "composition") and a solution of the polyfunctional acid halide in a water-immiscible organic solvent. The present invention is characterized in that an additive is incorporated into the above-mentioned composition so as to greatly improve the water flux of the semipermeable composite membrane.
-
- Among them, sodium alkyldiphenylether disulfonate, methylene-bis(sodium naphthalene-sulfonate) and sorbitol are preferred, and alkyldiphenyletherdisulfonic acid disodium salt is especially preferred because the performance of the composite semipermeable membrane is improved and it also acts as a surface active agent described below in the composition. In view of the surface-activating effect, a dodecyl group is preferred as the alkyl group, but practically, another alkyl group may be mixed with the dodecyl group, and two or more alkyl groups may be present.
- The effect is further enhanced by the addition of an alkaline metal compound such as trisodium phosphate.
- According to the preparation process of the present invention, the semipermeable composite membrane is prepared by coating the above-mentioned composition on at least one surface of a microporous substrate, air-drying and/or heating the coated membrane to evaporate a part or all of water, and coating a solution of a polyfunctional acid halide as the main component in a water immiscible organic solvent incapable of dissolving the porous substrate on the coated surface of membrane to undergo crosslinking reaction, followed by drying.
-
- The concentration of these components is 0.l to l0% by weight, preferable l to 4% by weight, and the mixing ratio between piperazine and l,3-di-(4-piperidyl)-propane is preferably such that the amount of l,3-di-(4-piperidyl)-propane is 0.05 to 0.5 part by weight per part by weight of piperazine. Furthermore, as pointed out hereinbefore, the mixing ratio between piperazine and the polyaminoether having recurring units of the formula [VII] is preferably such that the amount of the polyaminoether is 0.l to l.0 part by weight per part by weight of piperazine.
- In order to improve the wettability of the composition on the surface of the porous substrate and to adhere the composition uniformly to the surface, a surface active agent, especially an anionic surface active agent, may be added to the composition. For example, sodium dodecyl sulfate and sodium alkylbenzenesulfonate may be used, and alkyldiphenyletherdisulfonic acid disodium salt is especially effective for obtaining a membrane with good performance. Generally, the surface active agent is used in an amount of 0.0l to 4% by weight. A water-soluble organic solvent not degrading the microporous organic solvent may be added to the composition.
- Furthermore, addition of an alkaline metal salt, for example, a hydrochloric acid scavenger such as trisodium phosphate or sodium hydroxide, is effective for promoting the reaction between the secondary amine and the polyfunctional acid halide, and good effects are often obtained when a phase transfer catalyst or acylation catalyst is used in combination. Trisodium phosphate is especially preferred in view of the improvement of the water flux of the semipermeable composite membrane.
- In the present invention, any of polyfunctional acid halides capable of reacting with the secondary amine to form a crosslinked polyamide as the ultra-thin membrane can be used. For example, aromatic polyfunctional acid halides such as trimesoyl halide, benzophenonetetracarboxylic acid halide, trimellitic acid halide, pyromellitic acid halide, isophthaloyl halide, terephthaloyl halide, naphthalenedicarboxylic acid halide, diphenyldicarboxylic acid halide, pyridinedicarboxylic acid halide, benzenedisulfonyl halide, and chlorosulfonylisophthaloyl halides can be used. In view of the solubility in the membrane-forming solvent and the performance of the semipermeable composite membrane, trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride, and mixtures thereof are preferred.
- The mixing ratio of the acid chlorides is not particularly critical. However, in view of the water flux of the semipermeable composite membrane, the trimesoyl chloride/isophthaloyl chloride or trimesoyl chloride/terephthaloyl chloride weight ratio is preferably from l/0 to 3/7, and single use of isophthaloyl chloride or terephthaloyl chloride is not preferred in view of the water flux.
- The polyfunctional acid halide is generally used in the state dissolved in an organic solvent at a concentration of 0.0l to 2.0% by weight, preferably 0.l to 0.5% by weight.
- The organic solvent used in the present invention should be immiscible with water, be capable of dissolving the acid chloride therein, and not damage or destroy the microporous substrate and any organic solvent capable of providing a crosslinked polyamide by interfacial polymerization can be used.
- For example, hydrocarbon compounds, cyclohexane, and trichlorotrifluoroethane may be preferably used. In view of the reaction speed and the volatility of the solvent, at least one member selected from n-hexane and trifluorotrichloroethane is preferably used, and when the safety problem, that is, ignitability, is further taken into consideration, trichlorotrifluoroethane is especially preferred.
- Any known coating means can be adopted for coating the composition on the microporous supporting membrane. For example, there may be adopted a method in which the composition is coated on the substrate and a method in which the substrate is dipped in the composition. The method in which the composition is coated on the substrate is preferred because one surface of the microporous substrate can be uniformly coated with the composition and the operation can be easily accomplished. When the microporous substrate is dipped in the composition, it is preferable to adopt a means such that the composition does not adhere to the other surface of the microporous supporting membrane at the coating step. Generally, a liquid-removing step is arranged to remove the excessive composition applied at the coating step. As the liquid-removing means, there may be adoped, for example, a method in which the membrane surface is held vertically to allow the composition to naturally flow down.
- The coated porous substrate is air-dried or heated in an oven at room temperature to l50°C. The drying period is changed according to the drying method, that is, the manner of introduction of heat or the kind of oven drier, but the drying period is generally within the range of from 0.5 minute to 60 minutes. Then, the solution of the polyfunctional acid halide in the water-immiscible organic solvent is coated on the substrate and after the liquid-removing operation, the coated membrane is air-dried or heated to obtain a semipermeable composite membrane. The drying operation is ordinarily carried out at room temperature to l50°C, and the drying time is determined according to the drying temperature. This drying or heating treatment is effective for preventing peeling of the ultra-thin membrane from the microporous substrate.
- The so-obtained semipermeable composite membrane can be used as it is. However, the surface of the ultra-thin membrane of the semipermeable composite membrane can be covered with a protecting polymer membrane, and this protection is practically preferred. Application of the protective membrane on the surface of the ultra-thin membrane is accomplished by coating an appropriate polymer solution, followed by drying. As the protecting polymer, there can be mentioned, for example, water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, and polyvinyl pyrrolidone. In view of the strength of the protecting membrane, polyvinyl alcohol is especially preferred.
- The polymer is generally used in the form of an aqueous solution having a concentration of 0.5 to l0% by weight. Not only a dip-coating method but also a spray-coating method or a brush-coating method can be adopted for coating the polymer solution. The coated semipermeable composite membrane is dried in an oven to obtain a final product. It is generally preferred that the drying operation be carried out at 60 to l20°C for 2 to l0 minutes.
- The present invention will now be described in detail with reference to the following examples that by no means limit the scope of the invention.
- In the examples, the sodium chloride rejection as the selective separation capacity was determined according to the customary method of measuring the electroconductivity. Furthermore, the water flux as the permeation capacity was determined by measuring the amount of water permeation per unit area per unit hour.
- A taffeta having a size of 30 cm × 20 cm and composed of polyester fibers (both wefts and warps were l50-denier multifilament yarns, the weave density was 90 yarns/inch in the warp direction and 67 yarns/inch in the weft direction, and the thickness was l60 µm) was fixed to a glass plate and a dimethylformamide (DMF) solution containing l6% by weight of polysulfone (Udel P-3500 supplied by Union Carbide Corporation) was cast in a thickness of 200 µm on the taffeta at room temperature (20°C). The taffeta was immediately immersed in pure water and allowed to stand for 5 minutes to obtain a fiber-reinforced polysulfone substrate (hereinafter referred to as "FR-PS"). The pure water permeation coefficient of the so-obtained FR-PS (having a thickness of 2l0 to 2l5 µm) was 0.005 to 0.0l kg/cm²·sec·atm as determined under a pressure of l kg/cm² at 25°C.
- The FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 0.5% by weight of sodium dodecyl sulfate, and l.0% by weight of trisodium phosphate, and was air-dried at room temperature for 2 minutes. Then, the supporting membrane was coated with a solution formed by dissolving a mixture of isophthaloyl chloride/trimesoyl chloride (weight ratio = 2/l) in an amount of l.0 weight/volume% in trichlorotrifluoroethane and heat-treated at l00°C for 5 minutes.
- When the so-obtained composite membrane was subjected to the reverse osmosis test under a pressure of l5 kg/cm² at 25°C by using an aqueous solution containing 0.l5% of NaCl as the feed water for l4 hours, it was found that the salt rejection was 77% and the water flux was 2.4 m³/m²· day. When chlorine was added to this feed water and the test was carried out for 5 hours under conditions such that the residual chlorine concentration was l ppm and the pH value was 6.5, it was found that the salt rejection was 86% and the water flux was 2.2 m³/m²·day. Then, the residual chlorine was removed, and the operation was continued under the same conditions for l7 hours. It was found that the salt rejection was 86% and the water flux was 2.0 m³/m²·day, and it was confirmed that the chlorine resistance of the composite membrane was good.
- The FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 0.5% by weight of sodium dodecyl sulfate, and l.0% by weight of trisodium phosphate, and was dried for l minute at 70°C. Then, the supporting membrane was coated with a solution obtained by dissolving a mixture of isophthaloyl chloride/trimesoyl chloride (weight ratio = 2/l) in an amount of 0.5 weight/volume% in trichlorotrifluoroethane and was dried for 5 minutes with hot air at l00°C. Furthermore, sorbitol was added to the composition and the membrane preparation operation was conducted in the same manner as described above. The so-obtained composite membranes were subjected to the reverse osmosis test under the same conditions as Example l. The obtained results are shown in Table l.
- The FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 0.5% by weight of dodecyldiphenyletherdisulfonic acid disodium salt, and l.0% by weight of trisodium phosphate, and was dried for l minute with hot air at 70°C. Then, the substrate was coated with a solution obtained by dissolving 0.5%by weight of trimesoyl chloride in trichlorotrifluoroethane and heat-treated for 5 minutes at l00°C. When the reverse osmosis test was carried out under the same conditions as Example l, it was found that the salt rejection was 83% and the water flux was 2.3 m³/m²·day. When chlorine was added to the feed water so that the residual chlorine concentration was l ppm and the pH value was 6.5, and the test was conducted for 5 hours, it was found that the salt rejection was 94% and the water flux was 2.0 m³/m³·day. Then, the residual chlorine was removed and the operation was conducted for l7 hours under the same conditions. It was found that the salt rejection was 88% and the water flux was 2.0 m³/m²·day. As in the above-mentioned chlorine resistance test, hydrogen peroxide was added to feed water at a concentration of l.0%, the operation was conducted for 8 hours, and the hydrogen peroxide was then removed. Before the addition of hydrogen peroxide, the salt rejection was 83% and the water flux was 2.2m³/m²·day, and after the addition of hydrogen peroxide, the salt rejection was 87% and the water flux was 2.2m³/m²·day Thus, it was confirmed that the membrane performance was not substantially changed. Furthermore, the heat resistance was tested by immersing the membrane in hot water at 95°C for 4 hours. Before the heat resistance test, the salt rejection was 83% and the water salt rejection was 2.2m³/m²·day, and after the heat resistance test, the salt rejection was 82% and the water flux was 2.2m³/m²·day. It was found that the membrane performance was not substantially changed. Thus, it was confirmed that the membrane had good hydrogen peroxide resistance and good heat resistance.
- Furthermore, the reverse osmosis test was carried out under a pressure of l5 kg/cm² at 25°C by using an aqueous solution containing 0.l% of isopropyl alcohol as the feed water, and when the test was conducted for l2 hours, the isopropyl alcohol rejection was measured by gas chromatography. It was found that the rejection was 59%.
- Furthermore, an aqueous solution containing 0.2% of MgS0₄, 0.l5% of MgCl₂ or 0.2% of Na₂SO₄ was used as the feed water and the salt rejection was measured in the same manner as described above with respect to the removal of NaCl. The MgSO₄ rejection was 99.5%, the MgCl₂ rejection was 95%, and the Na₂SO₄ rejection was 99.9%.
- The FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidinyl)-propane, 0.3% by weight of water-soluble polyaminoether, 0.5% by weight of dodecyldiphenyletherdisulfonic acid disodium salt, and l.0% by weight of trisodium phosphate, and was dried for l minute with hot air at 70°C. Then, the membrane was coated with a solution of 5% by weight of trimesoyl chloride in trichlorotrifluoroethane and was heat-treated for 5 minutes with hot air at l00°C. When the so-obtained composite membrane was subjected to the reverse osmosis test under the same conditions as adopted in Example l, it was found that the salt rejection was 84% and the water flux was 2.7 m³/m²·day. Chlorine was added to the feed water so that the residual chlorine concentration was l ppm and the pH value was 6.5, and the test was conducted for 5 hours. It was found that the salt rejection was 94% and the water flux was 2.4 m³m²·day. The residual chlorine was removed and the operation was continued for l7 hours under the same conditions. It was found that the salt rejection was 90% and the water flux was 2.5 m³/m²·day. As in the above-mentioned chlorine resistance test, hydrogen peroxide was added to the feed water at a concentration of l.0% and the operation was conducted for 8 hours, and then, the hydrogen peroxide was removed. Before the addition of hydrogen peroxide, the salt rejection was 83% and the water flux was 2.6 m³/m²·day, and after the addition of hydrogen peroxide, the salt rejection was 85% and the water flux was 2.5 m³/m²·day. It was found that the performance of the membrane was not substantially changed.
- The preparation of the membrane and the reverse osmosis test were carried out under the same conditions as described in Example 8 except that the content of trisodium phosphate in the composition was changed to 2.0% by weight. It was found that the salt rejection was 62% and the water flux was 4.4 m³/m²·day.
- The FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.2% by weight of l,3-di-(4-piperidyl)-propane, 2.0% by weight of dodecyldiphenyletherdisulfonic acid disodium salt, and l.0% by weight of trisodium phosphate, and was dried for 30 seconds with hot air at 80°C. Then, the membrane was coated with a solution of 0.5% by weight of trimesoyl chloride in trichlorotrifluoroethane and was heat-treated for 5 minutes at l00°C. The obtained composite membrane was subjected to the reverse osmosis test under a pressure of 7.5 kg/cm² at a temperature of 25°C and a pH value 30of 6.5 by using an aqueous solution containing 0.05% of NaCl as the feed water. When the test was conducted for l6 hours, it was found that the salt rejection was 82% and the water was 2.l m³/m²·day
- The preparation of the membrane and the reverse osmosis test were carried out in the same manner as described in Example ll except that methylene-bis(sodium naphthalene-sulfonate) was used instead of dodecyldiphenyletherdisulfonic acid disodium salt. It was found that the salt rejection was 82% and the water flux was l.9 m³/m²·day.
- The preparation of the membrane and the reverse osmosis test were carried out in the same manner as described in Example ll except that acid chlorides shown in Table 2 were used and the concentration of dodecyldiphenyletherdisulfonic disodium salt was changed as shown in Table 2. The obtained results are shown in Table 2.
- The preparation of the membrane and the reverse osmosis test were carried out in the same manner as described in Example ll except that the acid chloride composition and the concentration of dodecyldiphenyletherdisulfonic acid disodium salt concentration were changed as indicated in Table 3. Then, chlorine was added to the feed water so that the residual chlorine concentration was l0 ppm and the pH value was 6.5, and the operation was conducted for l00 hours. Then, the residual chlorine was removed, and the performance of the membrane was tested. The obtained results are shown in Table 3.
- The procedures of Example l9 were repeated in the same manner except that 2% of hydrogen peroxide was added to the feed water instead of chlorine. The operation was conducted under a pressure of 2 kg/cm² for l2 hours and the hydrogen peroxide was removed. Then, the reverse osmosis test was carried out under a pressure of 7.5 kg/cm² at 25°C by using an aqueous solution containing 0.05% of NaCl as the feed water. The obtained results are shown in Table 4.
- The membrane prepared in the same manner as described in Example l4 was subjected to the chlorine resistance test. Namely, chlorine was added to a 0.05% NaCl aqueous solution as the feed water so that the residual chlorine content was l0 ppm and the pH value was 6.5, and the operation was conducted for l00 hours under a pressure of 7.5 kg/cm². Then, the residual chlorine content was changed to 50 ppm and the operation was conducted for ll5 hours. Then, the residual chlorine content was changed to l00 ppm and the operation was conducted for l20 hours. Before the addition of chlorine, the salt rejection was 82% and the water flux was 2.0 m³/m²·day, and after the addition of chlorine, the salt rejection was 80% and the water flux was l.8 m³/m²·day. No substantial deterioration of the membrane was observed.
-
- The composite membrane obtained in Example l4 was cut to an appropriate size and immersed in methylene chloride to separate the ultra-thin membrane layer from the supporting membrane. The ultra-thin membrane was recovered by suction filtration using a glass filter. Then, 30 mg of the recovered sample was hydrolyzed with l2 ml of 6N hydrochloric acid at l80°C. The liquid left after the removal of insoluble solids was dried to a solid state and the weight was measured. It was found that the weight was 25 mg. The solid was dissolved in a mixed solvent comprising 2 ml of methyl alcohol and l0 ml of ethyl ether and diazomethane was bubbled to the solution to esterify by methylation. The solvent was removed by distillation under reduced pressure, and 2 ml of methyl acetate and 0.5 ml of trifluoroacetic acid anhydride were added and left for 5 minutes. The solvent was removed by distillation under reduced pressure, the residue was dissolved in l ml of methyl alcohol, and the composition was analyzed by the GC-MS method.
- In the mass spectrum, peaks of molecular ions and fragment ions corresponding to trifluoroacetyl compounds of piperazine and l,3-di-(4-piperidyl)-propane, and methyl esters of trimesic acid and isophthalic acid were observed.
- According to the gas-chromatographical analysis using the internal reference method, it was found that the weight ratio of piperazine to l,3-di-(4-piperidyl)-propane was about l.0/0.2.
- The FR-PS obtained in the Referential Example was coated with an aqueous solution (composition) containing l.0% by weight of piperazine, 0.5% by weight of sodium dodecyl sulfate, and l.0% by weight of trisodium phosphate, and was dried at room temperature for 2 minutes. Then, a solution obtained by dissolving l.0 weight/volume% of a mixture(weight ratio = 2/l) of isophthaloyl chloride/trimesoyl chloride in n-hexane was coated on the membrane, followed by air drying. When the so-obtained composite membrane was subjected to the reverse osmosis test under a pressure of l5 kg/cm² at 25°C for l5 hours by using an aqueous solution containing 0.l5% of NaCl as the feed water, it was found that the salt rejection was 54% and the water flux was 2.8 m³/m²·day.
- The preparation of the membrane and the reverse osmosis test were carried out in the same manner as described in Comparative Example l except that trimesoyl chloride alone was used as the acid halide. It was found that the salt rejection was 47% and the water flux was l.8 m³/m²·day.
- The preparation of the membrane and the reverse osmosis test were carried out in the same manner as described in Comparative Example l except that trichlorofluoroethane was used instead of n-hexane as the solvent for the acid halide. It was found that the salt rejection ratio was 58% and the water flux was 2.4 m³/m²·day.
- The preparation of the membrane and the reverse osmosis test were carried out in the same manner as in Comparative Example 3 except that after coating of the trichlorofluoroethane solution of the acid halide, the coated membrane was heat-treated for 5 minutes at l00°C. It was found that the salt rejection was 55% and the water flux was 2.0 m³/m²·day.
- The preparation of the membrane and the reverse osmosis test were carried out in the same manner as described in Comparative Example 4 except that an aqueous solution containing l.0% by weight of l,3-di-(4-piperidyl)-propane, 0.5% by weight of sodium dodecyl sulfate and l.0% by weight of trisodium phosphate was used. It was found that the salt rejection was 64% and the water flux was 0.0l m³/m²·day.
- As apparent from the foregoing description, the composite membrane of the present invention is for selective permeation and separation of a specific component in a liquid mixture and is used for desalting brakish water or producing ultra pure water for the production of semiconductors. The composite membrane has a high desalting and high water flux such that can rarely be attained by the conventional techniques. Furthermore, a membrane having good chlorine resistance and good hydrogen peroxide resistance can be provided.
Claims (21)
and a solution of a polyfunctional acid halide in a water-immiscible organic solvent, wherein at least one member selected from the group consisting of compounds represented by the following formulae [IV], [V] and [VI]:
and
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- 1986-09-16 DE DE8686112706T patent/DE3675869D1/en not_active Expired - Fee Related
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Cited By (10)
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EP0227043A2 (en) * | 1985-12-19 | 1987-07-01 | Sumitomo Chemical Company, Limited | Composite semipermeable membrane and process for producing the same |
EP0227043A3 (en) * | 1985-12-19 | 1988-01-27 | Sumitomo Chemical Company, Limited | Composite semipermeable membrane and process for producing the same |
EP0316525A2 (en) * | 1987-11-18 | 1989-05-24 | The Dow Chemical Company | Polyamide reverse osmosis membranes |
EP0316525A3 (en) * | 1987-11-18 | 1990-05-16 | The Dow Chemical Company | Polyamide reverse osmosis membranes |
EP0465649A1 (en) * | 1990-01-26 | 1992-01-15 | Toray Industries, Inc. | Composite semipermeable membrane and production thereof |
EP0465649A4 (en) * | 1990-01-26 | 1992-07-01 | Toray Industries, Inc. | Composite semipermeable membrane and production thereof |
CN106018598A (en) * | 2016-05-19 | 2016-10-12 | 河南豫辰药业股份有限公司 | Method for measuring content of byproducts in difenidol hydrochloride intermediate N-(3-chloropropyl) piperidine |
EP3753969A1 (en) * | 2019-06-19 | 2020-12-23 | Rhodia Operations | Method for production of thermoplastic composites and their uses |
CN110756061A (en) * | 2019-10-12 | 2020-02-07 | 万华化学集团股份有限公司 | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof |
CN110756061B (en) * | 2019-10-12 | 2022-01-07 | 万华化学集团股份有限公司 | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
EP0217212B1 (en) | 1990-11-28 |
US4758343A (en) | 1988-07-19 |
EP0217212A3 (en) | 1987-11-04 |
DE3675869D1 (en) | 1991-01-10 |
US4857363A (en) | 1989-08-15 |
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